New sulfoderivatives of higher fatty acids and process of making same



Patented Mar. 29, 1932 UNITED STATES PATENT OFFICE GEORG 'KALISCHER, OF FRANKFORT-ON-THE-MAIN, AND KARL KELLER, OF FRANK- FORT-ON-THE-MAIN-FECHENHEIIVI, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE NEW SULFODERIVATIVES OF HIGHER FATTY ACIDS AND PROCESS OF MAKING SAME No Drawing. Application filed October 11, 1929, Serial No. 399,096, and in Germany November 6, 1928.

Our present invention relates to new sulfo-' derivatives of higher fatty acids. They are obtained by acting with an aqueous solution of a sulfite on a water soluble salt of a halogenated higher fatty acid of the general forwherein R means hydrogen .or hydroxyl, m o the number 1 or more, n a number more than 8 and w l or more. One may use as starting materials the water soluble salts of halogenated higher saturated, as well as unsaturated, fatty or hydroxyfatty acids. The reaction which may be carried out with or without addition of a catalyst such as copper or iodine salts, such as potassium iodide, occurs when heating the components under a reflux condenser. But for accelerating and completing the reaction advantageously, one may work in an autoclave at higher temperatures.

The water soluble salts of the halogenated fatty acidsused as starting materials may be advantageously produced in the same apparatus by adding previously the corresponding quantity of an acid binding agent to the free halogenated fatty acid. Or one may utilize an excess of the sulfite without without addition of a further acid binding agent, thus producing the salt of the halogenated fatty acid in situ during the course of the reaction; and We include in the following claims this step under the term water soluble salt of a higher halogenated fatty acid.

Apparently the smooth course of the re action is the more favored the more halogen atoms and hydroXyl-groups and double bonds are present in the molecule of the starting materials. In consequence thereof it is advisable to apply stronger conditions of reaction ,as to temperature, concentration of the components and duration of the reaction, when using halogenated fatty acids containing less halogen atoms or hydroxy-groups.

Very good and practicallv useful results are obtained, when starting from polyhalogenated fatty and particularly hydroxy-fatty acids containing at least four halogen atoms.

By our present reaction the halogen atoms of the starting materials are entirely or partly replaced by sulfonic acid groups. The fact that the new products of reaction contain a sulfonic acid group has been proved by analysis and by the test of hydrolizing the products by boiling with concentrated hydrochloric acid, whereby water soluble oils are obtained. In many cases the reaction products contain yet unchanged halogen atoms in their molecule. But the character of the end products of our present reaction allows the conclusion that, besides the formation of sulfonic acid groups in many cases a partial replacement of halogen by hydroxylgroups and a simultaneous polymerization of the fatty acid molecule in a more or less high degree may occur. Perhaps furthermore by splitting off halogen atoms new double bonds are formed.

When starting, for instance, either from a halogenated oleic, or stearic or ricinoleic acid derivative, we ascribe to the fundamental products of reaction the following general formula:

wherein R means hydrogen or hydroxyl, n the number 32 or 34, w the number zero or one or more, y the number one or more, m the number one or more.

According to the conditions applied to the starting material'used the new products of reaction are oils or semisolid or solid britstood that our invention is not limited to the 150 parts of water examples given, nor to the exact conditions stated therein. I

Example 1.43 parts of a tetrachlorostearic acid (obtainable by chl irinating stearic acid until the entrance of about four chlorine atoms per molecule has been effected) are mixed with 7 parts of potassium carbonate, about 100 parts of water and 80 parts of anhydrous potassium sulfite and the mixture is heatedin an autoclave for about 2-3 hours at about 130-150. The potassium salt of the sulfonated fatty acid thus obtained is separated from the reaction mass and may be purified by redissolving it in water and precipitating it by adding a salt solution. It represents a light oil soluble in water. It is distinguished by a good lime resistance andremains water soluble, when boiled with hot concentrated acids.

When starting from the same quantity of dibromostearic acid (obtainable by the addition of bromine to oleic acid) one may work as described above, but advantageously with the addition of about 4 parts of potassium iodide acting as catalyst and while increasing the reaction temperature to about 150-160; the product thus obtained may be separated from the remaining unsulfonated starting material. It corresponds in its properties with the above described reaction product.

Example 2.63.5 parts of a hexachlorinated stearic acid are mixed with 145 parts of anhydrous potassium sulfite and a solution of 7.3 parts of caustic potash in about The mixture is heated in an autoclave for some hours at about 130 to 140. The reaction product is worked up as described above. It shows properties similar to those of the product obtained according to Example 1.

Example 3.'65 parts of a chlorination product obtained by introducing about 6 chlorine atoms into the technical mixture of linoleic acids are transformed into the potassium salt in the form of an aqueous paste by admixture of a solution of 9.2 parts of fipotassium carbonate in 200 parts of water and stirred with 150 parts of anhydrous potassium sulfite. Then the mixture is heated about 140 to 150 while stirring. The reaction mass is then dissolved in a small quantity of'water and filtered. From the filtrate.

the sulfonationproduct separates after addition of common salt. It represents a feebly yellowish, viscous and water soluble oil of similar properties as described above.

In order to carry out the action of a sulfite on this hexachlororicinoleic acid, one may previously add a caustic soda solution and accordingly diminish the quantity of sodium sulfite. The reaction is favored by increasing gradually. the reaction temperature to about 200, while varying accordingly the concentration of the reacting agents.

\Vhen using 67 parts of a bromohydroxystearic acid or 70 parts of a bromodihydroxystearic acid (obtainable by the action of hydrobromic acid on oleic or ricinoleic acid respectively) as starting material and adding 14 parts of potassium carbonate in v 300 partsof water and 84 parts of potassium sulfite, one may advantageously work in an autoclave at about 140 to 145, preferably with addition of about 10-20 parts of potassium iodide. The potassium salts thus obtained may be separated from the salt solu tions and dissolved in water. By acidulation the free sulfocarboxylic acids are obtainable, which can be separated from unchanged starting material on account or their water solubility. The reaction products show similar properties as the above described products.

Example 5.63.5 parts of the same hexachlororicinoleic acid as used in the foregoing examples are mixed with 111 parts of anhydrous sodium sulfite and about 130 parts of water. Then the mixture is heated while stirring in an autoclave for several hours at about 140 to 150 in such a manner, that by simultaneously and slowly blowing off the water vapor the reaction mass becomes more concentrated. The reaction product which may be purified by redissolving in water and salting out represents a yellowlsh brittle and easily pulverable substance which is easily soluble in water and shows an increased resistance towards lime and acid and an' increased protective effect.

Example 6.- parts of a heptachloropalmitic acid are mixedwith 5.3 arts of sodium carbonate, 125 parts of sodium sulfite and about 250 parts of water and the mixture is boiled while stirring well for a longer time under a reflux condenser. Then the almost colorless reaction product is separated from the salt solution. It may be washed with a salt solution and purified in the above described manner. It shows a somewhat lower degree of sulfonation than the products of the foregoing examples, but corresponds otherwise in its properties therewith.

Example '7.81.5 parts of the colophony like chlorination product of ricinoleic acid obtained by chlorination in a carbontetrachloride solution and containing about sixteen chlorine atoms in its molecule are finely powdered and mixed to a paste by adding 6.5 parts of sodium carbonate, 150 parts of anhydrous sodium sulfite and about 200 parts of water. Then the mixture is heated slowly to about 140 while stirring in an autoclave. The reaction mass consists of two layers of an aqueous concentrated salt solution and the reaction product. When separated from the other layer, it is immediately applicable for technical purposes. Itforms. a gelatinous mass, is easily soluble in water and is distinguished by a particular resistance towards acids compared with the pi'oducts described in the foregoing examp es.

We claim:

1. A process which comprises acting with an aqueous solution of a sulfite on a water soluble salt of a halogenated higher fatty acid of the general formula:

n M r-z-m I wherein R means hydrogen or hydroxyl, m the number 1 or more, n a number more than 8 and a: 1 or more. v

2. A process which comprises acting with an aqueous solution of a sulfite in an autoclave at temperatures from 100 to 200 C. on a water soluble salt of a halogenated higher fatty acid of the general formula:

wherein R means hydrogen or hydroxyl, n the number 32 or 34, m and a: the number 1 or more.

4. A process which comprises acting with an aqueous solution of a sulfite in an autoclave at temperatures from 100 to 200 C. on a water soluble salt of a halogenated higher fatty acid of the general formula:

wherein R means hydrogen or hydroxyl, n the number 32 or 34, m the number 1 or more and w the number 4 or more.

A process which comprises acting with z: 11 aqueous solution of a sul te in an autoclave at temperatures from 100 to 200 C. on a or 34, m the number 1 or more and m the number 4 or more.

6. As new compounds derivatives of higher fatty acids containing a sulfonic acid group and corresponding otherwise probably to the general formula:

wherein n means a number more than 8 and w the number one or more, and m the number 1 or more which compounds are oils or semisolid or solid brittle, water soluble substances, characterized by the effect of protective colloids and by resistance towards acids and lime.

7. As new compounds derivatives of higher fatty acids containing a sulfonic acid group and corresponding otherwise probably to the general formula:

wherein n means the number 32 or 34, a: the number one or more and m the number one or more, which compounds are oils or semisolid or solid brittle, water soluble substances, characterized by the effect of protective c01- loids and by resistance towards acids and lime.

In testimony whereof, we aflix our signature's. GEORG KALISCHER. KARL KELLER.

water soluble salt of. a halogenated higher fatty acid of the general formula:

17 u-m-z m w' COOH wherein R- means hydroxyl, 'n, the number 35' 

